Process for synthesizing ionic metal complex

ABSTRACT

The invention relates to a process for synthesizing an ionic metal complex represented by the general formula (1) or (5). This process includes reacting in an organic solvent a compound (corresponding to ligand of the complex) represented by the general formula (2) or (6) with a halogen-containing compound represented by the general formula (3) or (4), in the presence of a reaction aid containing an element selected from the group consisting of elements of groups 1-4 and 11-14 of the periodic table. It is possible by this process to easily and efficiently synthesize the ionic metal complex, which can be used as a supporting electrolyte for electrochemical devices, a polymerization catalyst of polyolefins and so forth, or a catalyst for organic synthesis.

BACKGROUND OF THE INVENTION

[0001] The present invention relates to a process for synthesizing anionic metal complex that can be used as a supporting electrolyte forlithium batteries, lithium ion batteries, electrical double-layercapacitors and other electrochemical devices, a polymerization catalystfor polyolefins and so forth, or a catalyst for organic synthesis.

[0002] Ionic complexes, such as PF₆ ⁻, BF₄ ⁻ and AsF₆ ⁻, formed bybonding of Lewis acids with F ion have been used in applications such assupporting electrolytes for electrochemical devices, polymerizationcatalysts for polyolefins and so forth or catalysts for organicsynthesis due to their solubility and ion dissociation characteristicsand their high activity in reactions.

[0003] As the application range of these ionic complexes becomesincreasingly diverse, efforts are being made to search for the optimumionic complex for each application, and these ionic complexes are beingrequired to have properties including heat resistance, hydrolysisresistance, low toxicity and recycleability. Under such condition, therehave been proposed many complexes in which an organic ligand is bondedto the central element, in addition to conventional complexes in which asimple element (e.g., fluorine and oxygen) as a ligand is bonded to thecentral element.

[0004] There are various processes for synthesizing ionic complexes. Forexample, it is possible to use a neutralization reaction between (a) ahydroxide of an element corresponding to the central element and (b) aligand having an active hydrogen of a high acidity. As another example,it is possible to use a desalting reaction between (a) a halide of anelement corresponding to the central element and (b) a ligand (e.g.,alkali metals) having high degree of dissociation. Depending on thecombination of ligand and central element, however, reactivity maybecome too low to synthesize ionic complexes. Thus, it may becomedifficult to obtain the originally designed complexes.

SUMMARY OF THE INVENTION

[0005] It is an object of the present invention to provide a process foreasily and efficiently synthesizing an ionic metal complex.

[0006] According to the present invention, there is provided a firstprocess for synthesizing an ionic metal complex represented by thegeneral formula (1). The first process comprises reacting in an organicsolvent a compound represented by the general formula (2) with ahalogen-containing compound represented by the general formula (3) or(4), in the presence of a reaction aid comprising an element selectedfrom the group consisting of elements of groups 1-4 and 11-14 of theperiodic table,

[0007] According to the present invention, there is provided a secondprocess for synthesizing an ionic metal complex represented by thegeneral formula (5). The second process comprises reacting in an organicsolvent a compound represented by the general formula (6) with ahalogen-containing compound represented by the general formula (3) or(4), in the presence of a reaction aid comprising an element selectedfrom the group consisting of elements of groups 1-4 and 11-14 of theperiodic table,

[0008] In the general formulas (1) to (6), M represents a transitionmetal selected from the group consisting of elements of groups 3-11 ofthe periodic table, or an element selected from the group consisting ofelements of groups 12-15 of the periodic table;

[0009] A^(a+) represents a metal ion, hydrogen ion or onium ion;

[0010] a represents a number from 1 to 3; b represents a number from 1to 3; p is b/a; m represents a number from 1 to 4; n represents a numberfrom 0 to 8; q is 0 or 1;

[0011] each of R¹ and R² independently represents a hydrogen, halogen,C₁-C₁₀ alkyl group, or C₁-C₁₀ halogenated alkyl group;

[0012] R³ represents a C₁-C₁₀ alkylene group, C₁-C₁₀ halogenatedalkylene group, C₄-C₂₀ arylene group or C₄-C₂₀ halogenated arylenegroup, these alkylene and arylene groups of the R³ optionally havingsubstituents and hetero atoms, one of the R³ being optionally bondedwith another of the R³;

[0013] R⁴ represents a halogen, C₁-C₁₀ alkyl group, C₁-C₁₀ halogenatedalkyl group, C₄-C₂₀ aryl group, C₄-C₂₀ halogenated aryl group or X²R⁷,these alkyl and aryl groups of the R⁴ optionally having substituents andhetero atoms, one of the R⁴ being optionally bonded with another of theR⁴ to form a ring;

[0014] each of X¹, X² and X³ independently represents O, S, NR⁵ orNR⁵R⁶;

[0015] each of R⁵, R⁶ and R⁷ independently represents a hydrogen, C₁-C₁₀alkyl group, C₁-C₁₀ halogenated alkyl group, C₄-C₂₀ aryl group, orC₄-C₂₀ halogenated aryl group, these alkyl and aryl groups of the R⁵, R⁶and R⁷ optionally having substituents and hetero atoms, one of the R⁵being optionally bonded with another of the R⁵ to form a ring, one ofthe R⁶ being optionally bonded with another of the R⁶ to form a ring,one of the R⁷ being optionally bonded with another of the R⁷ to form aring;

[0016] each of E¹ and E² independently represents hydrogen or an alkalimetal; and

[0017] R⁸ represents a halogen.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] In the above general formulas, M is selected from elements ofgroups 3-15 of the periodic table. It is preferably Al, B, V, Ti, Si,Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf or Sb.

[0019] A^(a+) is a metal ion, hydrogen ion or onium ion. Preferably,A^(a+) is a lithium ion, quaternary alkylammonium ion or hydrogen ion.Specific examples of A^(a+) include lithium ion, sodium ion, potassiumion, magnesium ion, calcium ion, barium ion, cesium ion, silver ion,zinc ion, copper ion, cobalt ion, iron ion, nickel ion, manganese ion,titanium ion, lead ion, chromium ion, vanadium ion, ruthenium ion,yttrium ion, lanthanoid ion, actinoid ion, tetrabutylammonium ion,tetraethylammonium ion, tetramethylammonium ion, triethylmethylammoniumion, triethylammonium ion, pyridinium ion, imidazolium ion, hydrogenion, tetraethylphosphonium ion, tetramethylphosphonium ion,tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfoniumion and triphenylmethyl ion.

[0020] Valency (valence) of the A^(a+) cation is preferably from 1 to 3.If the valency is larger than 3, the problem occurs in which it becomesdifficult to dissolve the ionic metal complex in solvent due to theincrease in crystal lattice energy. Consequently, in the case ofrequiring solubility of the ionic metal complex, a valency of 1 ispreferable. As shown in the general formulas (1) and (5), the valency(b−) of the anion is similarly preferably from 1 to 3, and a valency of1 is particularly preferable. The constant p expresses the ratio of thevalency of the anion to the valency of the cation, namely b/a.

[0021] In the above general formulas, R³ is selected from C₁-C₁₀alkylene groups, C₁-C₁₀ halogenated alkylene groups, C₄-C₂₀ arylenegroups and C₄-C₂₀ halogenated arylene groups. These alkylene and arylenegroups may have substituents and hetero atoms in their structures. Forexample, the alkylene and arylene groups may have structures in whichhydrogen has been replaced with a substituent selected from halogens,chain-like or cyclic alkyl groups, aryl groups, alkenyl groups, alkoxygroups, aryloxy groups, sulfonyl groups, amino groups, cyano groups,carbonyl groups, acyl groups, amide groups, hydroxyl group and oxo group(═O). Furthermore, they may have structures in which carbon has beenreplaced with a substituent selected from nitrogen, sulfur and oxygen.When R³ exist in the plural number, they may be bonded together. Forexample, a ligand such as ethylenediaminetetraacetic acid can be cited.

[0022] R³ is preferably one that forms a 5 to 10-membered ring when achelate ring is formed with the central M. The case of a ring havingmore than 10 members is not preferable, since advantageous chelatingeffects are reduced. In addition, in the case that R³ has a portion ofhydroxyl group or carboxyl group, it is possible to form a bond betweenthe central M and this portion.

[0023] In the above general formulas, R⁴ is selected from halogens,C₁-C₁₀ alkyl groups, C₁-C₁₀ halogenated alkyl groups, C₄-C₂₀ arylgroups, C₄-C₂₀ halogenated aryl groups and X²R⁷. Similar to R³, thesealkyl and aryl groups may have substituents and hetero atoms in theirstructures. When R⁴ exist in the plural number, they may be bondedtogether to form a ring. R⁴ is preferably an electron attracting group,particularly fluorine. When R⁴ is fluorine, the degree of dissociationof the electrolyte is improved due to its strong electron attraction.Furthermore, mobility of the electrolyte is also improved due to thereduced size of the anionic moiety of the electrolyte. Therefore, theionic conductivity becomes very high when R⁴ is fluorine.

[0024] As mentioned above, each of X¹, X² and X³ in the above generalformulas independently represents O, S, NR⁵ or NR⁵R⁶. Thus, the ligandsare bonded to M with an interposal of these hetero atoms (O, S and N)therebetween. Although the bonding of an atom other than O, S or N isnot impossible, the synthesis becomes extremely bothersome.

[0025] The ionic metal complex represented by the general formula (1) ischaracterized by these ligands forming a chelate structure with M sincethere is bonding with M by X¹ and X³ within the same ligand. As a resultof this chelation, the heat resistance, chemical stability andhydrolysis resistance of the ionic metal complex are improved. Althoughconstant q in this ligand is either 0 or 1, in the case of 0 inparticular, since the chelate ring becomes a five-member ring, chelatingeffects are demonstrated most prominently, making this preferable due tothe resulting increase in stability.

[0026] In the above general formulas, each of R⁵, R⁶ and R⁷independently represents a hydrogen, C₁-C₁₀ alkyl group, C₁-C₁₀halogenated alkyl group, C₄-C₂₀ aryl group, or C₄-C₂₀ halogenated arylgroup. These alkyl and aryl groups optionally have substituents andhetero atoms. When R⁵, R⁶ and R⁷ are each exist in the plural number,each of R⁵, R⁶ and R⁷ may be formed into a ring.

[0027] Each of R⁵ and R⁶ differs from other groups (e.g., R¹ and R²) inthat the former is not required to be an electron attracting group. Inthe case of introducing an electron attracting group as R⁵ or R⁶, theelectron density on N of NR⁵R⁶ decreases, thereby preventingcoordination on the central M.

[0028] R⁷ is preferably a C₁-C₁₀ fluorinated alkyl group. Due to thepresence of an electron-attracting halogenated alkyl group as R⁷, thenegative charge of the central M is dissipated. Since this increases theelectrical stability of the anion of the general formula (1) or (5), iondissociation becomes extremely easy resulting in an increase of theionic metal complex in solvent solubility, ion conductivity and catalystactivity. In addition, other properties of heat resistance, chemicalstability and hydrolysis resistance are also improved. The case in whichthe halogenated alkyl group as R⁷ is a fluorinated alkyl group inparticular results in even greater advantageous effects.

[0029] For example, the alkyl and aryl groups of R⁷ may have structuresin which hydrogen has been replaced with a substituent selected fromhalogens, chain-like or cyclic alkyl groups, aryl groups, alkenylgroups, alkoxy groups, aryloxy groups, sulfonyl groups, amino groups,cyano groups, carbonyl groups, acyl groups, amide groups, hydroxyl groupand oxo group (═O). Furthermore, they may have structures in whichcarbon has been replaced with a substituent selected from nitrogen,sulfur and oxygen.

[0030] In the above general formulas, the values of the constants m andn relating to the number of the above-mentioned ligands depend on thetype of the central M. In fact, m is preferably from 1 to 4, while n ispreferably from 0 to 8.

[0031] Specific examples of the ionic metal complex represented by thegeneral formula (1) are as follows.

[0032] In the general formulas (5) and (6), each of R¹ and R² isindependently selected from H, halogen, C₁-C₁₀ alkyl groups and C₁-C₁₀halogenated alkyl groups. At least one of R¹ and R² is preferably afluorinated alkyl group, and more preferably, at least one of R¹ and R²is a trifluoromethyl group. Due to the presence of anelectron-attracting halogen and/or a halogenated alkyl group for R¹ andR², the negative charge of the central M is dissipated. This results inan increase of the anion of the general formula (5) in electricalstability. With this, the ion dissociation becomes extremely easyresulting in an increase of the ionic metal complex in solventsolubility, ion conductivity, catalyst activity and so forth. Inaddition, other properties of heat resistance, chemical stability andhydrolysis resistance are also improved. The case in which the halogenis fluorine in particular has significant advantageous effects, whilethe case of a trifluoromethyl group has the greatest advantageouseffect.

[0033] Specific examples of the ionic metal complex represented by thegeneral formula (5) are as follows.

[0034] The first or second process for synthesizing the ionic metalcomplex according to the present invention will be further explained inthe following. The first or second process is characterized in that acompound represented by the general formula (2) or (6) (corresponding toligand of the complex) is reacted with a halogen-containing compoundrepresented by the general formula (3) or (4) (a source of the centralelement M of the complex) in an organic solvent in the presence of aspecial reaction aid.

[0035] The compound represented by the general formula (2) or (6)contains E¹ and E² each independently being an active hydrogen or alkalimetal, for bonding the halogen R⁸ of the halogen-containing compoundwith E¹ and E² and then for eliminating the halogen R⁸. This compoundmay be classified as an alcohol, metal alkoxide, carboxylic acid,carboxylate, sulfonic acid, sulfonate, sulfinic acid, or sulfinate.

[0036] In the halogen-containing compound, at least one halogen isbonded with the central element M. In fact, this central element may bebonded with only halogens or with at least one halogen and at least oneother substituent. R⁸ is preferably fluorine. Specific examples of thehalogen-containing compound are LiPF₆, LiBF₄, LiAlCl₄, LiPF₃(CF₃)₃,LiBF₃(Ph), BF₃, and PF₅, where Ph represents a phenyl group.

[0037] As stated above, the reaction aid used in the first and secondprocesses contains an element selected from the group consisting ofelements of groups 1-4 and 11-14 of the periodic table, preferably theelements being Al, B, Si, alkali metals and alkali earth metals. Due toa strong bond between the element of the reaction aid and the halogen,the reaction aid can accelerate the reactions of the first and secondprocesses. The reaction aid is a compound preferably selected fromchlorides, bromides, iodides, alkoxides and carboxy compounds, morepreferably selected from AlCl₃, BCl₃ and SiCl₄.

[0038] When the compound represented by the general formula (2) or (6)(hereinafter the compound (2) or (6); other compounds may also bereferred to similarly) is mixed with the halogen-containing compound (3)or (4), small amounts of E¹R⁸ and E²R⁸ (by-products) are generated. Itis possible to remove these E¹R⁸ and E²R⁸ by the reaction aid. Withthis, the chemical equilibrium of the reactions of the first and secondprocesses changes towards the production of the target product. In otherwords, the reaction aid can accelerate these reactions. It is preferableto suitably select the compound (2) or (6) (corresponding to the ligandof the complex), the halogen-containing compound (3) or (4) (a source ofthe central atom M) and the reaction aid such that the by-products aresmoothly precipitated or smoothly removed as a high-vapor-pressurecomponent from the system.

[0039] Relative amounts of the reagents used in the reactions of thefirst and second processes are not particularly limited. It is possibleto use the compound (2) or (6) in an amount of 1-8 moles and thereaction aid in an amount of 0.1-10 moles, per mol of thehalogen-containing compound (3) or (4).

[0040] It is preferable to use a solvent in the reactions of the firstand second processes. This solvent is preferably one that is capable ofdissolving at least very small amounts of the raw materials and thatdoes not react with the compounds in the system. It is more preferablethat such solvent has a dielectric constant of 2 or greater. It is notpreferable to use a solvent having no such dissolving capacity, sincesuch solvent lowers the reaction rate. The reactions can proceed verysmoothly by using a solvent that is capable of dissolving at least verysmall amounts of the raw materials, since the target ionic metalcomplexes (1) and (5) have very high solubilities. The solvent can beselected from carbonates, esters, ethers, lactones, nitrites, amides,sulfones, alcohols, aromatic compounds, and mixtures of these. Itsspecific examples are propylene carbonate, ethylene carbonate, diethylcarbonate, dimethyl carbonate, methyl ethyl carbonate, dimethoxyethane,acetonitrile, propionitrile, tetrahydrofuran, 2-methyltetrahydrofuran,dioxane, nitromethane, N,N-dimethylformamide, dimethylsulfoxide,sulfolane, γ-butyrolactone, toluene, ethanol, and methanol.

[0041] The reaction temperature of the first and second processes may bein a range of −80 to 100° C., preferably 0 to 80° C. The reaction maynot proceed sufficiently with a reaction temperature lower than −80° C.The solvent and the raw materials may be decomposed with a reactiontemperature higher than 100° C. The reaction can proceed with asufficient reaction rate without no such decomposition, if the reactiontemperature is in a range of 0 to 80° C.

[0042] Some of the raw materials used in the first and second processesmay have a property to be hydrolyzed. Therefore, it is preferable toconduct the first and second processes in an atmosphere (e.g., air,nitrogen and argon) of low moisture content.

[0043] It is possible to purify the ionic metal complex, for example, bya recrystallization in which the reaction solution is concentrated toprecipitate the crystals or by a reprecipitation in which a large amountof a poor solvent is added to the reaction solution and then by washingthe resulting solid.

[0044] The following nonlimitative examples are illustrative of thepresent invention. Examples 1-1 to 1-6 are illustrative of the firstprocess of the present invention, and Examples 2-1 to 2-4 areillustrative of the second process of the present invention.

EXAMPLE 1-1

[0045] In a glove box having an atmosphere of a dew point of −50° C.,1.31 g of oxalic acid, 1.37 g of lithium tetrafluoroborate (LiBF₄), and20 ml of dimethylcarbonate were mixed together, followed by stirringsufficiently. With this, lithium tetrafluoroborate was dissolvedcompletely, but oxalic acid was not. Therefore, the mixture became inthe form of slurry. Then, 1.38 g of silicon tetrachloride (reaction aid)were slowly added to the mixture at room temperature with stirring. Atthe same time when this addition was started, a gas was generatedviolently. With this, the undissolved oxalic acid was dissolved, and thereaction proceeded. After the addition of silicon tetrachloride,stirring was continued for 3 hr. It was judged that the reaction hadterminated by confirming that the generation of the gas stoppedcompletely. Dimethyl carbonate was removed from the resulting reactionliquid at 40° C. under a reduced pressure of 133 Pa, thereby obtaining2.09 g of a white solid as a product. This product was washed with 20 mlof dimethyl ether, followed by solid separation with filtration and thendrying of the filtrate at 120° C. for 24 hr under a reduced pressure of133 Pa, thereby obtaining 2.09 g of lithium difluoro(oxalato)borate(yield: 99.5%) represented by the following formula.

EXAMPLE 1-2

[0046] In a glove box having an atmosphere of a dew point of −50° C.,1.31 g of oxalic acid, 1.37 g of lithium tetrafluoroborate (LiBF₄), and20 ml of dimethylcarbonate were mixed together, followed by stirringsufficiently. With this, lithium tetrafluoroborate was dissolvedcompletely, but oxalic acid was not. Therefore, the mixture became inthe form of slurry. Then, 1.30 g of aluminum trichloride (reaction aid)were slowly added to the mixture at room temperature with stirring. Atthe same time when this addition was started, a precipitate of a milkycolor was generated. After the addition of aluminum trichloride,stirring was continued for 3 hr. Then, the precipitate was separatedfrom the reaction liquid by filtration. Dimethyl carbonate was removedfrom the resulting reaction liquid at 40° C. under a reduced pressure of133 Pa, thereby obtaining 2.09 g of lithium difluoro(oxalato)borate(yield: 99.5%).

EXAMPLE 1-3

[0047] In a glove box having an atmosphere of a dew point of −50° C.,3.93 g of oxalic acid, 1.37 g of lithium tetrafluoroborate (LiBF₄), 0.76g of lithium fluoride, and 50 ml of ethyl methyl carbonate were mixedtogether, followed by stirring sufficiently. With this, lithiumtetrafluoroborate was dissolved completely, but oxalic acid and lithiumfluoride were not. Therefore, the mixture became in the form of slurry.Then, 3.03 g of trimethoxyborane ((CH₃O)₃B; reaction aid) were slowlyadded to the mixture at 0° C. with stirring. At the same time when thisaddition was started, the undissolved component started to dissolve. Atthe time when all the reagents were dissolved after the addition oftrimethoxyborane, ethyl methyl carbonate was removed from the resultingreaction liquid at 0° C. under a reduced pressure of 133 Pa, therebyobtaining 6.28 g of lithium difluoro(oxalato)borate (yield: 99.9%).

EXAMPLE 1-4

[0048] In a glove box having an atmosphere of a dew point of −50° C.,3.93 g of oxalic acid, 1.37 g of lithium tetrafluoroborate (LiBF₄), 0.76g of lithium fluoride, and 50 ml of ethyl methyl carbonate were mixedtogether, followed by stirring sufficiently. With this, lithiumtetrafluoroborate was dissolved completely, but oxalic acid and lithiumfluoride were not. Therefore, the mixture became in the form of slurry.Then, 3.43 g of boron trichloride (BCl₃; reaction aid) were slowly addedto the mixture at 0° C. with stirring. At the same time when thisaddition was started, the undissolved component started to dissolve andHCl gas started to form. At the time when all the reagents weredissolved after the addition of trimethoxyborane, ethyl methyl carbonatewas removed from the resulting reaction liquid at 30° C. under a reducedpressure of 133 Pa, thereby obtaining 6.28 g of lithiumdifluoro(oxalato)borate (yield: 99.9%).

EXAMPLE 1-5

[0049] In a glove box having an atmosphere of a dew point of −50° C.,1.31 g of oxalic acid, 2.21 g of lithium hexafluorophosphate (LiPF₆),and 20 ml of diethyl ether were mixed together, followed by stirringsufficiently. With this, oxalic acid and lithium hexafluorophosphatewere dissolved completely. Then, 1.38 g of silicon tetrachloride(reaction aid) were slowly added to the mixture at room temperature withstirring. At the same time when this addition was started, a gas wasgenerated violently and the reaction proceeded. After the addition ofsilicon tetrachloride, stirring was continued for 5 hr. It was judgedthat the reaction had terminated by confirming that the generation ofthe gas stopped completely and by confirming with NMR that the rawmaterials disappeared. The obtained reaction liquid was filtrated, andthen diethyl ether was removed from the resulting filtrate at 60° C.under a reduced pressure of 133 Pa, thereby obtaining 2.93 g of lithiumtetrafluoro(oxalato)phosphate represented by the following formula.

EXAMPLE 1-6

[0050] In a glove box having an atmosphere of a dew point of −50° C.,2.62 g of oxalic acid, 1.37 g of lithium tetrafluoroborate (LiBF₄), and50 ml of γ-butyrolactone were mixed together, followed by stirringsufficiently. With this, lithium tetrafluoroborate and oxalic acid weredissolved completely. Then, 2.75 g of silicon tetrachloride (reactionaid) were slowly added to the mixture at room temperature with stirring.At the same time when this addition was started, a gas was generatedviolently and the reaction proceeded. After the addition of silicontetrachloride, stirring was continued for 3 hr. It was judged that thereaction had terminated by confirming that the generation of the gasstopped completely. Then, γ-butyrolactone was removed from the resultingreaction liquid at 60° C. under a reduced pressure of 133 Pa, therebyobtaining a white solid as a product. This product was washed with 50 mlof dimethyl carbonate, followed by solid separation with filtration andthen drying of the filtrate at 120° C. for 24 hr under a reducedpressure of 133 Pa, thereby obtaining 2.81 g of lithiumbis(oxalato)borate (yield: 99.3%) represented by the following formula.

EXAMPLE 2-1

[0051] In a glove box having an atmosphere of a dew point of −50° C.,3.09 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CF₃)₂COOH), 1.37 g oflithium tetrafluoroborate (LiBF₄), and 20 ml of dimethyl carbonate weremixed together, followed by stirring sufficiently to dissolve thereagents. Then, 1.38 g of silicon tetrachloride (reaction aid) wereslowly added to the mixture at room temperature with stirring. At thesame time when this addition was started, a gas was generated violentlyand the reaction proceeded. After the addition of silicon tetrachloride,stirring was continued for 3 hr. It was judged that the reaction hadterminated by confirming that the generation of the gas stoppedcompletely. Dimethyl carbonate was removed from the resulting reactionliquid at 60° C. under a reduced pressure of 133 Pa, thereby obtaining3.87 g of a white solid as a product. This product is a lithium boratederivative represented by the following formula.

EXAMPLE 2-2

[0052] In a glove box having an atmosphere of a dew point of −50° C.,3.09 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CF₃)₂COOH), 1.37 g oflithium tetrafluoroborate (LiBF₄), and 20 ml of diethyl carbonate weremixed together, followed by stirring sufficiently to dissolve thereagents. Then, 1.30 g of aluminum trichloride (reaction aid) wereslowly added to the mixture at room temperature with stirring. At thesame time when this addition was started, a precipitate of a milky colorwas generated. After the addition of aluminum trichloride, stirring wascontinued for 3 hr. Then, the precipitate was separated from thereaction liquid by filtration. Diethyl carbonate was removed from theresulting reaction liquid at 80° C. under a reduced pressure of 133 Pa,thereby obtaining 3.79 g of the same lithium borate derivative as thatof Example 2-1.

EXAMPLE 2-3

[0053] In a glove box having an atmosphere of a dew point of −50° C.,3.08 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CF₃)₂COOH), 2.21 g oflithium hexafluorophosphate (LiPF₆), and 20 ml of dimethyl carbonatewere mixed together, followed by stirring sufficiently to dissolve thereagents. Then, 1.38 g of silicon tetrachloride (reaction aid) wereslowly added to the mixture at room temperature with stirring. At thesame time when this addition was started, a gas was generated violentlyand the reaction proceeded. After the addition of silicon tetrachloride,stirring was continued for 5 hr. It was judged that the reaction hadterminated by confirming that the generation of the gas stoppedcompletely and by confirming with NMR that the raw materialsdisappeared. The obtained reaction liquid was filtrated, and theresulting filtrate was dried at 60° C. under a reduced pressure of 133Pa, thereby obtaining 2.93 g of a lithium phosphate derivativerepresented by the following formula.

EXAMPLE 2-4

[0054] In a glove box having an atmosphere of a dew point of −50° C.,6.18 g of hexafluoro-2-hydroxyisobutyric acid (HOC(CF₃)₂COOH), 1.37 g oflithium tetrafluoroborate (LiBF₄), and 50 ml of acetonitrile were mixedtogether, followed by stirring sufficiently to dissolve the reagents.Then, 2.75 g of silicon tetrachloride (reaction aid) were slowly addedto the mixture at room temperature with stirring. At the same time whenthis addition was started, a gas was generated violently and thereaction proceeded. After the addition of silicon tetrachloride,stirring was continued for 3 hr. It was judged that the reaction hadterminated by confirming that the generation of the gas stoppedcompletely. Acetonitrile was removed from the obtained reaction liquidat 60° C. under a reduced pressure of 133 Pa, thereby obtaining alithium borate derivative represented by the following formula.

What is claimed is:
 1. A process for synthesizing an ionic metal complexrepresented by the general formula (1), the process comprising reactingin an organic solvent a compound represented by the general formula (2)with a halogen-containing compound represented by the general formula(3) or (4), in the presence of a reaction aid comprising an elementselected from the group consisting of elements of groups 1-4 and 11-14of the periodic table,

wherein M represents a transition metal selected from the groupconsisting of elements of groups 3-11 of the periodic table, or anelement selected from the group consisting of elements of groups 12-15of the periodic table; A^(a+) represents a metal ion, hydrogen ion oronium ion; a represents a number from 1 to 3; b represents a number from1 to 3; p is b/a; m represents a number from 1 to 4; n represents anumber from 0 to 8; q is 0 or 1; R³ represents a C₁-C₁₀ alkylene group,C₁-C₁₀ halogenated alkylene group, C₄-C₂₀ arylene group or C₄-C₂₀halogenated arylene group, these alkylene and arylene groups of the R³optionally having substituents and hetero atoms, one of the R³ beingoptionally bonded with another of the R³; R⁴ represents a halogen,C₁-C₁₀ alkyl group, C₁-C₁₀ halogenated alkyl group, C₄-C₂₀ aryl group,C₄-C₂₀ halogenated aryl group or X²R⁷, these alkyl and aryl groups ofthe R⁴ optionally having substituents and hetero atoms, one of the R⁴being optionally bonded with another of the R⁴ to form a ring; each ofX¹, X² and X³ independently represents O, S, NR⁵ or NR⁵R⁶; each of R⁵,R⁶ and R⁷ independently represents a hydrogen, C₁-C₁₀ alkyl group,C₁-C₁₀ halogenated alkyl group, C₄-C₂₀ aryl group, or C₄-C₂₀ halogenatedaryl group, these alkyl and aryl groups of the R⁵ and R⁷ optionallyhaving substituents and hetero atoms, one of the R⁵ being optionallybonded with another of the R⁵ to form a ring, one of the R⁷ beingoptionally bonded with another of the R⁷ to form a ring; each of E¹ andE² independently represents a hydrogen or alkali metal; and R⁸represents a halogen.
 2. A process according to claim 1, wherein thereaction aid is a compound of an element selected from the groupconsisting of Al, B, Si, alkali metals and alkali earth metals.
 3. Aprocess according to claim 2, wherein the compound is selected from thegroup consisting of chlorides, bromides, iodides, alkoxides and carboxycompounds.
 4. A process according to claim 3, wherein the compound isAlCl₃, BCl₃ or SiCl₄.
 5. A process according to claim 1, wherein the Mis an element selected from the group consisting of Al, B, V, Ti, Si,Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf, and Sb.
 6. Aprocess according to claim 1, wherein the A^(a+) is a lithium ion,quaternary alkylammonium ion or proton. 7 A process according to claim1, wherein the R⁸ is fluorine.
 8. A process for synthesizing an ionicmetal complex represented by the general formula (5), the processcomprising reacting in an organic solvent a compound represented by thegeneral formula (6) with a halogen-containing compound represented bythe general formula (3) or (4), in the presence of a reaction aidcomprising an element selected from the group consisting of elements ofgroups 1-4 and 11-14 of the periodic table,

wherein M represents a transition metal selected from the groupconsisting of elements of groups 3-11 of the periodic table, or anelement selected from the group consisting of elements of groups 12-15of the periodic table; A^(a+) represents a metal ion, hydrogen ion oronium ion; a represents a number from 1 to 3; b represents a number from1 to 3; p is b/a; m represents a number from 1 to 4; n represents anumber from 0 to 8; q is 0 or 1; each of R¹ and R² independentlyrepresents a hydrogen, halogen, C₁-C₁₀ alkyl group, or C₁-C₁₀halogenated alkyl group; R³ represents a C₁-C₁₀ alkylene group, C₁-C₁₀halogenated alkylene group, C₄-C₂₀ arylene group or C₄-C₂₀ halogenatedarylene group, these alkylene and arylene groups of the R³ optionallyhaving substituents and hetero atoms, one of the R³ being optionallybonded with another of the R³; R⁴ represents a halogen, C₁-C₁₀ alkylgroup, C₁-C₁₀ halogenated alkyl group, C₄-C₂₀ aryl group, C₄-C₂₀halogenated aryl group or X²R⁷, these alkyl and aryl groups of the R⁴optionally having substituents and hetero atoms, one of the R⁴ beingoptionally bonded with another of the R⁴ to form a ring; each of X¹ andX² independently represents O, S, NR⁵ or NR⁵R⁶; each of R⁵, R⁶ and R⁷independently represents a hydrogen, C₁-C₁₀ alkyl group, C₁-C₁₀halogenated alkyl group, C₄-C₂₀ aryl groups of the R⁵, R⁶ and R⁷optionally having substituents and hetero atoms, one of the R⁵ beingoptionally bonded with another of the R⁵ to form a ring, one of the R⁶being optionally bonded with another of the R⁶ to form a ring, one ofthe R⁷ being optionally bonded with another of the R⁷ to form a ring;each of E¹ and E² independently represents a hydrogen or alkali metal;and R⁸ represents a halogen.
 9. A process according to claim 8, whereinthe reaction aid is a compound of an element selected from the groupconsisting of Al, B, Si, alkali metals and alkali earth metals.
 10. Aprocess according to claim 9, wherein the compound is selected from thegroup consisting of chlorides, bromides, iodides, alkoxides and carboxycompounds.
 11. A process according to claim 10, wherein the compound isAlCl₃, BCl₃ or SiCl₄.
 12. A process according to claim 8, wherein the Mis an element selected from the group consisting of Al, B, V, Ti, Si,Zr, Ge, Sn, Cu, Y, Zn, Ga, Nb, Ta, Bi, P, As, Sc, Hf, and Sb.
 13. Aprocess according to claim 8, wherein the A^(a+) is a lithium ion,quaternary alkylammonium ion or proton.
 14. A process according to claim8, wherein the R⁸ is fluorine.